Functionalized elastomer

ABSTRACT

The present invention is directed to a stereoregular functionalized elastomer represented by poly(M1 co M2), wherein the functionalized elastomer comprises a microstructure selected from the group consisting of microstructures having at least 90 percent by weight of monomer residues in trans 1,4-configuration, and microstructures having at least 80 percent by weight of monomer residues in cis 1,4-configuration; wherein M1 is selected from the group consisting of isoprene and 1,3-butadiene; and M2 is of formula 4 
     
       
         
         
             
             
         
       
     
     wherein R 6  is a covalent bond, phenylene, a linear or branched alkane diyl group containing 1 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; R 7  is hydrogen or a linear or branched alkyl group containing 1 to 10 carbon atoms; X 1  is selected from formulas 5 and 6 
     
       
         
         
             
             
         
       
     
     wherein R 8  and R 9  are independently trialkylsilyl, phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or one of R 8  and R 9  is hydrogen and the other is phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R 8  and R 9  taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; and X 2  is a sulfur atom or a structure of formula 7 or 8 
     
       
         
         
             
             
         
       
     
     wherein when X 2  is of formula 8, the S atom of formula 8 is adjacent to the phenyl ring of formula 6 and the N atom of formula 8 is adjacent to R 6 .

BACKGROUND OF THE INVENTION

To produce stereoregular polymers, catalytic insertion polymerization is the method of choice. Resulting stereoregular poly(1-olefins) and poly(dienes) are of enormous practical importance. An introduction of polar groups in such stereoregular polymerizations is challenging, however, due to the sensitivity of most catalysts towards heteroatom-containing substrates. An introduction of polar and reactive groups in the polymer backbone and into the end-groups in particular is desirable to enhance the compatibility with polar surface, like e.g. metals or fillers and for cross-linking. Concerning an incorporation into the polymer chain, recent work has resulted in an advance towards stereoregular polar functionalized poly(propylene) (Nozaki et al., Angew. Chem., Int. Ed. 2016, 55, (26), 7505-7509.) For poly(dienes), insertion polymerization of functionalized dienes and other pathways to stereoregular poly(dienes) have been reported (Leicht et al., S. ACS Macro Lett. 2016, 5, (6), 777-780; Leicht et al., Polym. Chem. 2016; Cui et al., Polym. Chem. 2016, 7, (6), 1264-1270.) Examples for syntheses of chain-end functionalized poly(dienes) are so far based on methods like anionic polymerization (Quirk et al., Polymer 2004, 45, (3), 873-880; Stewart et al., British Polymer Journal 1990, 22, (4), 319-325.) or ring opening metathesis polymerization (Hillmyer et al., Macromolecules 1997, 30, (4), 718-721; Ji et al., Macromolecules 2004, 37, (15), 5485-5489; Chung et al., Macromolecules 1992, 25, (20), 5137-5144) that do not provide access to stereoregular polymers. There remains a need for a method to produce stereoregular polymers functionalized with polar groups.

SUMMARY OF THE INVENTION

Most lanthanide-based catalyst precursors for stereoselective diene polymerization require activation by a second reagent, often organo-metal compounds. The present invention includes the usage of polar functionalized organo-metal activators for the synthesis of chain-end functionalized stereoregular dienes. Further, the combination of this method with the generation of functionalized chain-ends by quenching at the end of the polymerization and direct copolymerization with functionalized dienes gives access to stereoregular, trifunctional, hetero-telechelic poly(dienes).

The preparation of stereoregular poly(dienes) with functional groups in the main chain as well as in both end-groups, the later in a hetero-telechelic fashion is disclosed. A key element is the finding that Nd-based trans-selective systems for diene polymerization are tolerant towards different functional groups based on nitrogen or sulfur. Further, activation of Nd(BH₄)₃.(THF)₃ proceeds with functionalized magnesium alkyls to introduce functional groups at the initiating chain-ends. At the terminating chain-end, an end-group could be generated by conversion of reactive metal-carbon bonds present in the catalyst system with suitable quenching reagents. Notably, all three elements are compatible with one another and can be carried out together, i.e. stereoregularity or the nature of the reactive metal-polymeryl bonds are not compromised by the presence of functional activators or monomers.

Stereoregular poly(dienes) with three different functional groups were synthesized by insertion polymerization. The functional groups are located simultaneously in the polymer backbone and at both chain ends, yielding hetero-telechelic and in-chain functionalized polymers. A combination of three compatible functionalization methods allows for the syntheses of these particular polymers. Nd(BH₄)₃.(THF)₃ catalyzes, after activation with MgR₂, the direct copolymerization of 1,3-butadiene or isoprene with polar functionalized dienes, thus enabling the functionalization of the polymer's backbone. The use of functionalized organo-Mg compounds, like (PhS—C₅H₁₀)₂Mg, for the activation of Nd(BH₄)₃.(THF)₃ enables the functionalization of one chain-end and quenching of the polymerization with suitable reagents like Si(OEt)₄ allows for the functionalization of the other chain-end. While activation of Nd(BH₄)₃.(THF)₃ with MgR₂ initiates usually a 1,4-trans selective diene polymerization, the use of polar organo-Mg compounds as activation reagents has also been shown to be a viable method for chain-end functionalization in cis-selective diene polymerizations.

The present invention therefore involves the use of functional magnesium-based chain transfer reagants that impart functionality on the end of every chain end. By combining this technique with known functionalization techniques such as termination with functional terminators or copolymerization with functional monomers, the invention describes a method to make stereoregular polymers that contain functionality on both ends, as well as in-chain. Either high-cis or high-trans polymers can be made through changes to the catalyst system, without affecting the functionalization reactions.

The present invention is directed to a stereoregular functionalized elastomer represented by poly(M1 co M2), wherein the functionalized elastomer comprises a microstructure selected from the group consisting of microstructures having at least 90 percent by weight of monomer residues in trans 1,4-configuration, and microstructures having at least 80 percent by weight of monomer residues in cis 1,4-configuration; wherein M1 is selected from the group consisting of isoprene and 1,3-butadiene; and M2 is of formula 4

wherein R⁶ is a covalent bond, phenylene, a linear or branched alkane diyl group containing 1 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; R⁷ is hydrogen or a linear or branched alkyl group containing 1 to 10 carbon atoms; X¹ is selected from formulas 5 and 6

wherein R⁸ and R⁹ are independently trialkylsilyl, phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or one of R⁸ and R⁹ is hydrogen and the other is phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R⁸ and R⁹ taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; and X² is a sulfur atom or a structure of formula 7 or 8

wherein when X² is of formula 8, the S atom of formula 8 is adjacent to the phenyl ring of formula 6 and the N atom of formula 8 is adjacent to R⁶.

There is further disclosed a rubber composition comprising the functionalized elastomer, and a tire comprising the rubber composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows FIG. 1: ¹H NMR spectrum of a BD/3 copolymer (Table 1-A, entry 7, recorded at 27° C. in C₆D₆).

FIG. 2: ¹H NMR spectrum of a poly(isoprene) sample with triethoxysilyl end-groups (Table 1, entry 5, recorded at 27° C. in C₆D₆).

FIG. 3: ¹H and 1D-TOCSY NMR spectra of a copolymer synthesized from isoprene and comonomer 3, showing the connectivity of the butyl chain and the poly(isoprene) backbone (Table 1, entry 10, recorded at 27° C. in C₆D₆). Irradiation at 1 (250 ms mixing time) results in excitation of signals 2, 3, 4, 5, and even 6 by magnetization transfer through bonds, proving the attachment of the butyl moiety to the PIP-backbone.

FIG. 4: ¹H NMR spectrum and according DOSY NMR traces of chain-end functionalized poly(butadiene) sample. The sample was obtained by a polymerization activated with Mg-5 (Table 2, entry 8, spectra recorded at 27° C. in C₆D₆).

FIG. 5: ¹H NMR spectrum of a trifunctionalized, hetero-telechelic poly(isoprene) sample (recorded at 27° C. in C₆D₆).

FIG. 6: ¹H NMR spectrum and according DOSY NMR traces of a trifunctionalized, hetero-telechelic poly(butadiene) sample, proving the connection of all different functional groups to the polymer backbone (recorded at 27° C. in C₆D₆).

DETAILED DESCRIPTION OF THE INVENTION

There is disclosed a stereoregular functionalized elastomer represented by poly(M1 co M2), wherein the functionalized elastomer comprises a microstructure selected from the group consisting of microstructures having at least 90 percent by weight of monomer residues in trans 1,4-configuration, and microstructures having at least 80 percent by weight of monomer residues in cis 1,4-configuration; wherein M1 is selected from the group consisting of isoprene and 1,3-butadiene; and M2 is of formula 4

wherein R⁶ is a covalent bond, phenylene, a linear or branched alkane diyl group containing 1 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; R⁷ is hydrogen or a linear or branched alkyl group containing 1 to 10 carbon atoms; X¹ is selected from formulas 5 and 6

wherein R⁸ and R⁹ are independently trialkylsilyl, phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or one of R⁸ and R⁹ is hydrogen and the other is phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R⁸ and R⁹ taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; and X² is a sulfur atom or a structure of formula 7 or 8

wherein when X² is of formula 8, the S atom of formula 8 is adjacent to the phenyl ring of formula 6 and the N atom of formula 8 is adjacent to R⁶.

The functionalized elastomer is made via a polymerization utilizing a lanthanide based catalyst system. Suitable catalysts include neodymium based catalysts, including neodymium borohydride complexes activated with dialkylmagnesium compounds, and neodymium carboxylates activated with dialkylmagnesium compounds and alkyl aluminum chlorides.

Such polymerizations are typically conducted in a hydrocarbon solvent that can be one or more aromatic, paraffinic, or cycloparaffinic compounds. These solvents will normally contain from 4 to 10 carbon atoms per molecule and will be liquids under the conditions of the polymerization. Some representative examples of suitable organic solvents include pentane, isooctane, cyclohexane, normal hexane, benzene, toluene, xylene, ethylbenzene, and the like, alone or in admixture.

In one embodiment, the neodymium catalyst system is a neodymium borohydride activated with a functional dialkyl magnesium compound. In one embodiment, the neodymium borohydride is Nd(BH₄)₃.(THF)₃ where THF is tetrahydrofuran. Suitable functional dialkyl magnesium compounds included compound of formula 1

Q-R¹—Mg—R¹-Q  1

where R¹ is phenylene, or a linear or branched alkane diyl group containing 2 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; Q is of formula 2 or I3

—S—R²  2

where R2 is phenyl, or a linear or branched alkyl group containing 2 to 10 carbon atoms;

where R³ and R⁴ are independently phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R² and R³ taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms.

In one embodiment, the neodymium catalyst system used in the process of this invention is made by preforming three catalyst components. These components are (1) the functional dialkyl magnesium compound of formula I, (2) a neodymium carboxylate, and (3) an alkyl aluminum chloride. In making the neodymium catalyst system the neodymium carboxylate and the alkyl aluminum chloride compound are first reacted together for 10 seconds to 30 minutes in the presence of isoprene or butadiene to produce a neodymium-aluminum catalyst component. The neodymium carboxylate and the organoaluminum compound are preferable reacted for 2 minutes to 30 minutes and are more preferable reacted for 3 to 25 minutes in producing the neodymium-aluminum catalyst component.

The neodymium-aluminum catalyst component is then reacted with the functional dialkyl magnesium compound to yield the active catalyst system.

The neodymium catalyst system will typically be pre-formed at a temperature that is within the range of about 0° C. to about 100° C. The neodymium catalyst system will more typically be prepared at a temperature that is within the range of about 10° C. to about 60° C.

The neodymium carboxylate utilizes an organic monocarboxylic acid ligand that contains from 1 to 20 carbon atoms, such as acetic acid, propionic acid, valeric acid, hexanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, stearic acid and the like neodymium naphthenate, neodymium neodecanoate, neodymium octanoate, and other neodymium metal complexes with carboxylic acid containing ligands containing from 1 to 20 carbon atoms.

The concentration of the total catalyst system employed of course, depends upon factors such as purity of the system, polymerization rate desired, temperature and other factors. Therefore, specific concentrations cannot be set forth except to say that catalytic amounts are used.

Temperatures at which the polymerization reaction is carried out can be varied over a wide range. Usually the temperature can be varied from extremely low temperatures such as −60° C. up to high temperatures, such as 150° C. or higher. Thus, the temperature is not a critical factor of the invention. It is generally preferred, however, to conduct the reaction at a temperature in the range of from about 10° C. to about 90° C. The pressure at which the polymerization is carried out can also be varied over a wide range. The reaction can be conducted at atmospheric pressure or, if desired, it can be carried out at sub-atmospheric or super-atmospheric pressure. Generally, a satisfactory polymerization is obtained when the reaction is carried out at about autogenous pressure, developed by the reactants under the operating conditions used.

Examples of useful functional dialkyl magnesium compounds of formula 1 include but are not limited to compounds such as the following

The polymerization can be quenched or terminated by the addition of a functional terminator, an alcohol or another protic source, such as water.

In one embodiment, the polymerization is terminated using a functional terminator. By functional terminator, it is meant an organic compound capable of terminating the polymerization reaction, wherein the organic compound is substituted with a functional group comprising at least one heteroatom selected from phosphorus, boron, oxygen, halogens and silicon.

In one embodiment, the functional terminator comprises at least one functional group selected from the group consisting of phosphane, phosphonic acid, phosphate, phosphodiester, phosphotriester, silyl, alklysilyl, alkoxysilyl, and siloxy.

Useful functional terminators include but are not limited to tetraethoxysilane, n-octyltriethoxysilane, 3-chloropropyltriethoxysilane, and chlorodiphenylphosphine.

Suitable monomers for use in the polymerization are conjugated diene monomers and functionalized versions thereof. Suitable conjugated diene monomers include 1,3-butadiene and isoprene. Other suitable conjugated diene monomers include 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, and the like, and combinations thereof.

In one embodiment, the monomer includes a functionalized monomer of formula 4

wherein R⁶ is a covalent bond, phenylene, a linear or branched alkane diyl group containing 1 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; R⁷ is hydrogen or a linear or branched alkyl group containing 1 to 10 carbon atoms; X¹ is selected from formulas 5 and 6

wherein R⁸ and R⁹ are independently trialkylsilyl, phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or one of R⁸ and R⁹ is hydrogen and the other is phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R⁸ and R⁹ taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; and X² is a sulfur atom or a structure of formula 7 or 8

wherein when X² is of formula 8, the S atom of formula 8 is adjacent to the phenyl ring of formula 6 and the N atom of formula 8 is adjacent to R⁶.

In one embodiment, the nitrogen containing heterocyclic group is selected from the group consisting of the structures

wherein R⁵ groups can be the same or different and represent a member selected from the group consisting of linear or branched alkyl groups containing from 1 to about 10 carbon atoms, aryl groups, allyl groups, and alkoxy groups, and wherein Y represents oxygen, sulfur, or a methylene group, and n is an integer from 4 to 12.

In one embodiment, suitable functionalized monomers are selected from the following monomer structures

where in monomer 3, TMS refers to a trimethylsilyl group.

The use of functional magnesium-based chain transfer reagents of formula 1 imparts functionality on the end of every polymer chain end. By combining the technique with known functionalization techniques such as termination with functional terminators or copolymerization with functional monomers, the polymerization results in stereoregular polymers that contain functionality on both ends, as well as in-chain. Either high-cis or high-trans polymers can be made through changes to the catalyst system, without affecting the functionalization reactions. By stereoregular, it is meant that the polymer microstructure includes at least 80 percent by weight of monomer residues (i.e., polymer subunits derived from a given monomer) in the cis 1,4-configuration, or 90 percent by weight of monomer residues in the trans 1,4-configuration. In one embodiment, the polymer contains at least 85 percent by weight of monomer residues in cis 1,4-configuration. In one embodiment, the polymer contains at least 95 percent by weight of monomer residues in trans 1,4-configuration.

A stereoregular functionalized elastomer so produced may be represented by poly(M1 co M2), wherein the functionalized elastomer comprises a microstructure selected from the group consisting of microstructures having at least 90 percent by weight of monomer residues in trans 1,4-configuration, and microstructures having at least 80 percent by weight of monomer residues in cis 1,4-configuration; wherein M1 is selected from the group consisting of isoprene and 1,3-butadiene; and M2 is of formula 4.

The copolymer functionalized elastomer of the invention may be compounded into a rubber composition.

The rubber composition may optionally include, in addition to the copolymer, one or more rubbers or elastomers containing olefinic unsaturation. The phrases “rubber or elastomer containing olefinic unsaturation” or “diene based elastomer” are intended to include both natural rubber and its various raw and reclaim forms as well as various synthetic rubbers. In the description of this invention, the terms “rubber” and “elastomer” may be used interchangeably, unless otherwise prescribed. The terms “rubber composition,” “compounded rubber” and “rubber compound” are used interchangeably to refer to rubber which has been blended or mixed with various ingredients and materials and such terms are well known to those having skill in the rubber mixing or rubber compounding art. Representative synthetic polymers are the homopolymerization products of butadiene and its homologues and derivatives, for example, methylbutadiene, dimethylbutadiene and pentadiene as well as copolymers such as those formed from butadiene or its homologues or derivatives with other unsaturated monomers. Among the latter are acetylenes, for example, vinyl acetylene; olefins, for example, isobutylene, which copolymerizes with isoprene to form butyl rubber; vinyl compounds, for example, acrylic acid, acrylonitrile (which polymerize with butadiene to form NBR), methacrylic acid and styrene, the latter compound polymerizing with butadiene to form SBR, as well as vinyl esters and various unsaturated aldehydes, ketones and ethers, e.g., acrolein, methyl isopropenyl ketone and vinylethyl ether. Specific examples of synthetic rubbers include neoprene (polychloroprene), polybutadiene (including cis-1,4-polybutadiene), polyisoprene (including cis-1,4-polyisoprene), butyl rubber, halobutyl rubber such as chlorobutyl rubber or bromobutyl rubber, styrene/isoprene/butadiene rubber, copolymers of 1,3-butadiene or isoprene with monomers such as styrene, acrylonitrile and methyl methacrylate, as well as ethylene/propylene terpolymers, also known as ethylene/propylene/diene monomer (EPDM), and in particular, ethylene/propylene/dicyclopentadiene terpolymers. Additional examples of rubbers which may be used include alkoxy-silyl end functionalized solution polymerized polymers (SBR, PBR, IBR and SIBR), silicon-coupled and tin-coupled star-branched polymers. The preferred rubber or elastomers are polyisoprene (natural or synthetic), polybutadiene and SBR.

In one aspect the at least one additional rubber is preferably of at least two of diene based rubbers. For example, a combination of two or more rubbers is preferred such as cis 1,4-polyisoprene rubber (natural or synthetic, although natural is preferred), 3,4-polyisoprene rubber, styrene/isoprene/butadiene rubber, emulsion and solution polymerization derived styrene/butadiene rubbers, cis 1,4-polybutadiene rubbers and emulsion polymerization prepared butadiene/acrylonitrile copolymers.

In one aspect of this invention, an emulsion polymerization derived styrene/butadiene (E-SBR) might be used having a relatively conventional styrene content of about 20 to about 28 percent bound styrene or, for some applications, an E-SBR having a medium to relatively high bound styrene content, namely, a bound styrene content of about 30 to about 45 percent.

By emulsion polymerization prepared E-SBR, it is meant that styrene and 1,3-butadiene are copolymerized as an aqueous emulsion. Such are well known to those skilled in such art. The bound styrene content can vary, for example, from about 5 to about 50 percent. In one aspect, the E-SBR may also contain acrylonitrile to form a terpolymer rubber, as E-SBAR, in amounts, for example, of about 2 to about 30 weight percent bound acrylonitrile in the terpolymer.

Emulsion polymerization prepared styrene/butadiene/acrylonitrile copolymer rubbers containing about 2 to about 40 weight percent bound acrylonitrile in the copolymer are also contemplated as diene based rubbers for use in this invention.

The solution polymerization prepared SBR (S—SBR) typically has a bound styrene content in a range of about 5 to about 50, preferably about 9 to about 36, percent. The S—SBR can be conveniently prepared, for example, by organo lithium catalyzation in the presence of an organic hydrocarbon solvent.

In one embodiment, cis 1,4-polybutadiene rubber (BR) may be used. Such BR can be prepared, for example, by organic solution polymerization of 1,3-butadiene. The BR may be conveniently characterized, for example, by having at least a 90 percent cis 1,4-content.

The cis 1,4-polyisoprene and cis 1,4-polyisoprene natural rubber are well known to those having skill in the rubber art.

The term “phr” as used herein, and according to conventional practice, refers to “parts by weight of a respective material per 100 parts by weight of rubber, or elastomer.”

The rubber composition may also include up to 70 phr of processing oil. Processing oil may be included in the rubber composition as extending oil typically used to extend elastomers. Processing oil may also be included in the rubber composition by addition of the oil directly during rubber compounding. The processing oil used may include both extending oil present in the elastomers, and process oil added during compounding. Suitable process oils include various oils as are known in the art, including aromatic, paraffinic, naphthenic, vegetable oils, and low PCA oils, such as MES, TDAE, SRAE and heavy naphthenic oils. Suitable low PCA oils include those having a polycyclic aromatic content of less than 3 percent by weight as determined by the IP346 method. Procedures for the IP346 method may be found in Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62nd edition, published by the Institute of Petroleum, United Kingdom.

The rubber composition may include from about 10 to about 150 phr of silica. In another embodiment, from 20 to 80 phr of silica may be used.

The commonly employed siliceous pigments which may be used in the rubber compound include conventional pyrogenic and precipitated siliceous pigments (silica). In one embodiment, precipitated silica is used. The conventional siliceous pigments employed in this invention are precipitated silicas such as, for example, those obtained by the acidification of a soluble silicate, e.g., sodium silicate.

Such conventional silicas might be characterized, for example, by having a BET surface area, as measured using nitrogen gas. In one embodiment, the BET surface area may be in the range of about 40 to about 600 square meters per gram. In another embodiment, the BET surface area may be in a range of about 80 to about 300 square meters per gram. The BET method of measuring surface area is described in the Journal of the American Chemical Society, Volume 60, Page 304 (1930).

The conventional silica may also be characterized by having a dibutylphthalate (DBP) absorption value in a range of about 100 to about 400, alternatively about 150 to about 300.

The conventional silica might be expected to have an average ultimate particle size, for example, in the range of 0.01 to 0.05 micron as determined by the electron microscope, although the silica particles may be even smaller, or possibly larger, in size.

Various commercially available silicas may be used, such as, only for example herein, and without limitation, silicas commercially available from PPG Industries under the Hi-Sil trademark with designations 210, 243, etc; silicas available from Rhodia, with, for example, designations of Z1165MP and Z165GR and silicas available from Degussa AG with, for example, designations VN2 and VN3, etc.

Commonly employed carbon blacks can be used as a conventional filler in an amount ranging from 10 to 150 phr. In another embodiment, from 20 to 80 phr of carbon black may be used. Representative examples of such carbon blacks include N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991. These carbon blacks have iodine absorptions ranging from 9 to 145 g/kg and DBP number ranging from 34 to 150 cm³/100 g.

Other fillers may be used in the rubber composition including, but not limited to, particulate fillers including ultra-high molecular weight polyethylene (UHMWPE), crosslinked particulate polymer gels including but not limited to those disclosed in U.S. Pat. Nos. 6,242,534; 6,207,757; 6,133,364; 6,372,857; 5,395,891; or 6,127,488, and plasticized starch composite filler including but not limited to that disclosed in U.S. Pat. No. 5,672,639. Such other fillers may be used in an amount ranging from 1 to 30 phr.

In one embodiment, the rubber composition may contain a conventional sulfur containing organosilicon compound. In one embodiment, the sulfur containing organosilicon compounds are the 3,3′-bis(trimethoxy or triethoxy silylpropyl) polysulfides. In one embodiment, the sulfur containing organosilicon compounds are 3,3′-bis(triethoxysilylpropyl) disulfide and/or 3,3′-bis(triethoxysilylpropyl) tetrasulfide.

In another embodiment, suitable sulfur containing organosilicon compounds include compounds disclosed in U.S. Pat. No. 6,608,125. In one embodiment, the sulfur containing organosilicon compounds includes 3-(octanoylthio)-1-propyltriethoxysilane, CH₃(CH₂)₆C(═O)—S—CH₂CH₂CH₂Si(OCH₂CH₃)₃, which is available commercially as NXT™ from Momentive Performance Materials.

In another embodiment, suitable sulfur containing organosilicon compounds include those disclosed in U.S. Patent Publication No. 2003/0130535. In one embodiment, the sulfur containing organosilicon compound is Si-363 from Degussa.

The amount of the sulfur containing organosilicon compound in a rubber composition will vary depending on the level of other additives that are used. Generally speaking, the amount of the compound will range from 0.5 to 20 phr. In one embodiment, the amount will range from 1 to 10 phr.

It is readily understood by those having skill in the art that the rubber composition would be compounded by methods generally known in the rubber compounding art, such as mixing the various sulfur-vulcanizable constituent rubbers with various commonly used additive materials such as, for example, sulfur donors, curing aids, such as activators and retarders and processing additives, such as oils, resins including tackifying resins and plasticizers, fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants and peptizing agents. As known to those skilled in the art, depending on the intended use of the sulfur vulcanizable and sulfur-vulcanized material (rubbers), the additives mentioned above are selected and commonly used in conventional amounts. Representative examples of sulfur donors include elemental sulfur (free sulfur), an amine disulfide, polymeric polysulfide and sulfur olefin adducts. In one embodiment, the sulfur-vulcanizing agent is elemental sulfur. The sulfur-vulcanizing agent may be used in an amount ranging from 0.5 to 8 phr, alternatively with a range of from 1.5 to 6 phr. Typical amounts of tackifier resins, if used, comprise about 0.5 to about 10 phr, usually about 1 to about 5 phr. Typical amounts of processing aids comprise about 1 to about 50 phr. Typical amounts of antioxidants comprise about 1 to about 5 phr. Representative antioxidants may be, for example, diphenyl-p-phenylenediamine and others, such as, for example, those disclosed in The Vanderbilt Rubber Handbook (1978), Pages 344 through 346. Typical amounts of antiozonants comprise about 1 to 5 phr. Typical amounts of fatty acids, if used, which can include stearic acid comprise about 0.5 to about 3 phr. Typical amounts of zinc oxide comprise about 2 to about 5 phr. Typical amounts of waxes comprise about 1 to about 5 phr. Often microcrystalline waxes are used. Typical amounts of peptizers comprise about 0.1 to about 1 phr. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.

Accelerators are used to control the time and/or temperature required for vulcanization and to improve the properties of the vulcanizate. In one embodiment, a single accelerator system may be used, i.e., primary accelerator. The primary accelerator(s) may be used in total amounts ranging from about 0.5 to about 4, alternatively about 0.8 to about 1.5, phr. In another embodiment, combinations of a primary and a secondary accelerator might be used with the secondary accelerator being used in smaller amounts, such as from about 0.05 to about 3 phr, in order to activate and to improve the properties of the vulcanizate. Combinations of these accelerators might be expected to produce a synergistic effect on the final properties and are somewhat better than those produced by use of either accelerator alone. In addition, delayed action accelerators may be used which are not affected by normal processing temperatures but produce a satisfactory cure at ordinary vulcanization temperatures. Vulcanization retarders might also be used. Suitable types of accelerators that may be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. In one embodiment, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator may be a guanidine, dithiocarbamate or thiuram compound.

The mixing of the rubber composition can be accomplished by methods known to those having skill in the rubber mixing art. For example, the ingredients are typically mixed in at least two stages, namely, at least one non-productive stage followed by a productive mix stage. The final curatives including sulfur-vulcanizing agents are typically mixed in the final stage which is conventionally called the “productive” mix stage in which the mixing typically occurs at a temperature, or ultimate temperature, lower than the mix temperature(s) than the preceding non-productive mix stage(s). The terms “non-productive” and “productive” mix stages are well known to those having skill in the rubber mixing art. The rubber composition may be subjected to a thermomechanical mixing step. The thermomechanical mixing step generally comprises a mechanical working in a mixer or extruder for a period of time suitable in order to produce a rubber temperature between 140° C. and 190° C. The appropriate duration of the thermomechanical working varies as a function of the operating conditions, and the volume and nature of the components. For example, the thermomechanical working may be from 1 to 20 minutes.

The rubber composition may be incorporated in a variety of rubber components of the tire. For example, the rubber component may be a tread (including tread cap and tread base), sidewall, apex, chafer, sidewall insert, wirecoat or innerliner. In one embodiment, the component is a tread.

The pneumatic tire of the present invention may be a race tire, passenger tire, aircraft tire, agricultural, earthmover, off-the-road, truck tire, and the like. In one embodiment, the tire is a passenger or truck tire. The tire may also be a radial or bias.

Vulcanization of the pneumatic tire of the present invention is generally carried out at conventional temperatures ranging from about 100° C. to 200° C. In one embodiment, the vulcanization is conducted at temperatures ranging from about 110° C. to 180° C. Any of the usual vulcanization processes may be used such as heating in a press or mold, heating with superheated steam or hot air. Such tires can be built, shaped, molded and cured by various methods which are known and will be readily apparent to those having skill in such art.

This invention is illustrated by the following examples that are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight.

Example 1

Homopolymerizations of BD were performed to optimize polymerization conditions for high stereoselectivity and to assess the influence of the diene:Nd ratio on the molecular weights and molecular weight distributions of the obtained polymers. 5 μmol Nd(BH₄)₃.(THF)₃ were activated with 1 equiv. of MgBuz in the presence of different amounts of BD in toluene (Table 1, entries 1-3). Polymerization at 60° C. for 5 h yielded in all cases highly stereoregular 1,4-trans-PBD (>95 mol % trans-units). The molecular weights of the obtained polymers are close to the theoretically calculated molecular weights (for a polymerization where only one polymer chain per Nd is formed) and increase linearly with increasing BD:Nd ratio. Although GPC analyses indicate a bimodal molecular weight distribution (cf. SI), all molecular weight distributions are narrow (Mw/Mn=1.3-1.6). Hence, a controlled character of the polymerization can be assumed. DSC analyses of the polymers gave the typically two distinct melting points for high 1,4-trans-PBD. Not only butadiene but also isoprene is stereoselectively polymerized. A polymerization of isoprene in an NMR tube gives poly(isoprene) with 95% 1,4-trans units (Table 1, entry 4). The narrow molecular weight distribution and a molecular weight close to the theoretical value also indicate a controlled polymerization of isoprene. Having established the general polymerization behavior under our conditions of the catalyst system based on Nd(BH₄)₃.(THF)₃, three different approaches for the functionalization of the obtained stereoregular poly(diene) were explored: 1) The direct introduction of polar groups into the backbone of the polymer by insertion copolymerization of butadiene or isoprene with polar functionalized dienes. 2) The functionalization of one chain-end by reaction of the reactive metal-carbon bond with a suitable quenching reagent. 3) The functionalization of the other chain-end by using polar functionalized Mg-compounds.

TABLE 1 (Co)polymerizations of butadiene and isoprene catalyzed by Nd(BH₄)₃•(THF)₃ activated with MgBu₂. yield comon. comon. M_(n) ^(b)) 1,4-trans- cat. time diene comon. [mg] incorp.^(a)) conv. [10³ g T_(m) ^(c)) content^(d)) entry [μmol] [h] [mmol] [μmol] (%) [mol %] [%] mol⁻¹] M_(w)/M_(n) ^(b)) [°C.] [%] 1  5 5  4.6 BD — 202 (81) — — 43 1.3 45/94 95 2  5 5  9.2 BD — 440 (89) — — 89 1.6 45/98 97 3  5 5 13.8 BD — 698 (94) — — 133 1.4 46/98 95 4 20 3   2 IP — 125 (92) — — 7.7 1.5 n.d. 95 5 ^(f)) 60 2.5   6 IP — 330 (81) — 12 1.5 n.d. 93 6 ^(g)) 60 3   6 IP — 411 (99) — 5.8 1.3 n.d. 95 Polymerization conditions: Nd(BH₄)₃•(THF)₃:MgBu₂ = 1:1, T = 60° C. in toluene ^(a))determined by ¹HNMR ^(b))determined by GPC in THF vs. PS standards. ^(c))determined by DSC ^(d))determined by ¹³C NMR e) incorporation not determined because comonomer incorporation signals are overlapped by the polymer backbone. ^(f)) quenched with 600 μmol Si(OEt)₄ ^(g)) quenched with 600 μmol Ph₂PCl.

Example 2

Copolymerization with Polar Functionalized Dienes.

The functional group tolerance of Nd(BH₄)₃.(THF)₃ activated with MgR₂ in diene polymerizations was tested with comonomers 1-5 (Table 1-A, entries 7-12).

Chart 1: Polar functionalized dienes used in copolymerizations with butadiene and isoprene.

TABLE 1-A yield comon. comon. M_(n) ^(b)) 1,4-trans- cat. time diene comon. [mg] incorp.^(a)) conv. [10³ g T_(m) ^(c)) content^(d)) entry [μmol] [h] [mmol] [μmol] (%) [mol %] [%] mol⁻¹] M_(w)/M_(n) ^(b)) [°C.] [%]  7  5 5 4.6 BD 150 152 (61) 1 3.9 73 43 1.8 50/72 94  8  5 5 4.6 BD 170 195 (79) 2 n.d.^(e)) n.d.^(e)) 46 1.6 48/93 94  9  5 5 4.6 BD 150 222 (89) 3 3.6 99 44 3.0 47/61 94 10 60 5 6.2 IP 430 484 (92) 3 7.2 99 7.7 1.3 n.d. 96 11  5 5 4.6 BD  0.16 208 4 3.4 82 43 1.9 50/73 93 12  5 5 4.6 BD  0.15 196 5 3.3 80 47 3.0 49/71 93 Polymerization conditions: Nd(BH₄)₃•(THF)₃:MgBu₂ = 1:1, T = 60° C. in toluene ^(a))determined by ¹HNMR ^(b))determined by GPC in THF vs. PS standards. ^(c))determined by DSC ^(d))determined by ¹³C NMR ^(e))incorporation not determined because comonomer incorporation signals are overlapped by the polymer backbone. f) quenched with 600 μmol Si(OEt)₄ g) quenched with 600 μmol Ph₂PCl.

Comparison of the copolymerizations with a BD homopolymerization under otherwise identical conditions reveals no to little adverse impact of the comonomer present on yield, molecular weight and stereoselectivity (e.g. Table 1, 1-A, entry 1 vs. 7). Copolymerizations with 3 and 5 result in polymers with broader molecular weight distributions. Additionally, copolymers of 1 and 3 exhibit a lowered second melting point. Incorporation of 1 and 3 proceeds efficiently (73% and 99% comonomer conversion) and yields copolymers with incorporations of 3.9 mol % and 3.6 mol % respectively (FIG. 1). The incorporation ratio of the copolymer synthesized from butadiene and 2 could not be determined unequivocally because all proton signals of the propyl side chain (most indicative PhS—CH₂—) are overlapped by signals of the poly(butadiene) backbone (Table 1, entry 8). In contrast, the signal of the PhS—CH₂-group is shifted in copolymers with 4 and 5, allowing again for detection and determination of the comonomer incorporation (3.4 and 3.3 mol %, Table 1, entries 11 and 12). The formation of true copolymers was, additionally to ¹H NMR experiments, undoubtedly established by extensive NMR analyses of the polymers including 1D TOCSY, 2D and DOSY experiments.

These polymerizations prove that Nd(BH₄)₃.(THF)₃ activated with MgR₂ is a viable catalyst system for the direct copolymerization of butadiene or isoprene with functionalized dienes to polar functionalized 1,4-trans-poly(dienes).

Example 3

Chain-End Functionalization by Quenching.

The second part of the functionalization strategy aims at the reaction of reactive metal-carbon bonds present with a suitable quenching reagent (Scheme 1).

We tested four different quenching reagents, Si(OEt)₄, Ph₂PCl, B(OEt)₃, and P(O)(OEt)₃ towards their reactivity with the aforementioned metal-carbon bonds. For this purpose, polymerizations run with an IP:Nd ratio of 100:1 were terminated by the addition of the quenching reagents (cf. Table 1, entries 5 and 6, for examples with Si(OEt)₄ and Ph₂PCl). The reaction mixture was stirred at the polymerization temperature until it became colorless. The polymers were isolated by precipitation in dry acetonitrile (polymers quenched with Si(OEt)₄, B(OEt)₃, or P(O)(OEt)₃) or acidified MeOH (Ph₂PCl-modified) followed by drying under reduced pressure. To verify the functionalization by quenching, the polymers were subjected to a thorough analysis by means of NMR spectroscopy. ¹H and ¹³C NMR showed no indication for a successful functionalization for polymers quenched with B(OEt)₃ or P(0)(OEt)₃. In contrast, the polymer quenched with Si(OEt)₄ exhibits characteristic shifts for an ethoxy-moiety in the ¹H NMR spectrum at δ=3.89 ppm and δ=1.20 ppm (FIG. 2). The assignment of these signals to a SiOCH₂CH₃ group is substantiated by ¹H-¹³C-HSQC NMR spectroscopy revealing the corresponding carbon shifts at δ=59.4 ppm and 17.8 ppm. A connectivity of these ethoxy moieties to the poly(isoprene) backbone was probed by 1D TOCSY and DOSY NMR spectroscopy. The formation of ethoxysilyl endgroups is unambiguously proven by DOSY-NMR. Both, the SiOCH₂CH₃ group as well as the backbone signals exhibit the same diffusion coefficient, i.e. both correlate to a species with a comparable molecular weight, this would not be the case for e.g BuSi(OEt)₃ which could likely be formed from the reaction of residual RMgBu with Si(OEt)₄.

A quantitative view on the end-group functionalization reveals that the reaction does not proceed quantitatively, with quenching efficiencies (i.e. portion of chains functionalized) between 40 and 50%.

A polymer quenched with Ph₂PCl at the end of the polymerization reaction exhibits characteristic ¹H NMR shifts in the aromatic region at δ=7.81-6.90 ppm, indicating a successful functionalization of the polymer. Although this assumption is substantiated by the observation of signals in the ³¹P NMR spectrum, the presence of at least seven different ³¹P species, however, points to a low selectivity or the occurrence of side reactions. Still, DOSY-NMR establishes the connection of the aromatic protons to the poly(isoprene) backbone in terms of identical diffusion coefficients and thus a successful functionalization.

Example 4

Chain-End Functionalization by Activation with Functionalized Mg-Reagents.

The third functionalization strategy targets the introduction of functional groups via the use of functional activation reagents, i.e. organo-magnesium compounds. This functionalization would result in poly(dienes) with polar end groups (Scheme 2).

Before we started to assess the potential of this approach towards a possible functionalization of the polymer chain-end, we tested our polymerization conditions in terms of this method's general ability to transfer organic moieties from Mg to Nd and eventually to the chain-end with a non-functionalized alkyl group, i.e. an n-butyl moiety through transfer from MgBu₂. The presence of n-butyl end-groups was observed by the appearance of a ¹H NMR signal with a shift typical for aliphatic —CH₃ groups (δ=0.90 ppm) for all polymerizations in which MgBu₂ was used as activation reagent.

A detailed NMR analysis to prove the presence of a butyl group as chain-end was performed for a copolymer synthesized from IP and 3. TOCSY irradiation at the resonance of the CH₃ group results in magnetization transfer along the residual butyl chain up to the aliphatic and olefinic signals of the first isoprene unit in the backbone (FIG. 3). This outcome was further substantiated by DOSY-NMR, also showing the attachment of the butyl moiety to the PIP backbone.

Example 5

Having established the possibility to introduce a chain-end by transferring an organic group from Mg to Nd, we engaged in the synthesis of different polar functionalized organo-Mg compounds (Chart 2).

Chart 2: Polar functionalized organo-magnesium compounds used for the activation of Nd-based catalyst systems.

Polar functionalized organo-Mg compounds Mg-1 to Mg-5 were synthesized by reacting the according Br- or Cl-compound, e.g. Cl—C₅H₁₀—SPh for Mg-5, with activated Mg to form the mono-alkyl Mg compound ClMg—C₅H₁₀—SPh. The di-alkyl Mg compound Mg(C₅H₁₀—SPh)₂, Mg-5, was then formed by shifting the Schlenk equilibrium towards MgR₂/MgCl₂ upon addition of dioxane. Removal of MgX₂ gave the desired magnesium compounds Mg-1 to Mg-5 in good to high yields with the saturated species, e.g. C₅H₁₁—SPh, as a side product. There is no need, however, to remove the saturated species because they have no adverse influence on the intended use of the synthesized organo-Mg compounds.

Example 6

Polymerizations with a Nd:diene ratio of ca. 1:100 were performed to assess the general ability of Mg-x (x=1-5) to activate Nd(BH₄)₃.(THF)₃ for the trans-selective diene polymerization. The low Nd:diene ratio was chosen to ensure an end-group to backbone ratio sufficiently high for subsequent NMR analyses. Activation of Nd(BH₄)₃. (THF)₃ was successful with all different polar functionalized organo-Mg compounds. This includes not only the activation by Mg-alkyl compounds (Mg-1, Mg-4, and Mg-5) but also the activation by Mg-aryl compounds (Mg-2 and Mg-3).

TABLE 2 Results of diene polymerizations activated with polar functionalized organo-magnesium compounds. activation yield funct. groups M_(n) ^(c)) 1,4-trans- Nd diene time activation efficiency^(d)) [mg] in polymer^(b)) [10³ g content^(d)) entry [μmol] [mmol] [h] reagent [%] (%) [mol %] mol^(−1]) M_(w)/M_(n) ^(c)) [%]  1 ^(e)) 60   6 IP  2.5 Mg-1 94 373 (91) 1.5 10.8 3.2 93  2 20   2 IP  2.5 Mg-1 92 116 (85) 1.1 7.4 1.8 93  3 60   6 IP  5 Mg-2 n.d.^(f)) 324 (79) n.d.^(f)) 16.5 2.8 92  4 60   6 IP  5.5 Mg-3 42 350 (86) 0.5 18.8 4.8 91  5 50 4.6 BD  5 Mg-3 58 140 (56) 1.1 n.d. n.d. 94  6 50   5 IP 72 Mg-4 42 282 (83) 0.5 14.2 4.1 95  7 50 4.6 BD  3 Mg-4 32 106 (43) 0.8 17 2.4 93  8 50 4.6 BD  5 Mg-5 92 112 (45) 2.2 5.1 1.8 94  9  5 4.6 BD  5 Mg-4 n.d.^(g)) 150 (60) n.d.^(g)) 57 2.8 95 10  5 4.6 BD  5 Mg-5 n.d.^(g)) 185 (74) n.d.^(g)) 48 3.0 94 Polymerization conditions: Nd(BH₄)₃•(THF)₃:MgR₂ = 1:1, T = 60° C. in toluene or C₆D₆ ^(a))activation efficiency = (funct. groups in polymer in mol % · 100⁻¹) · (n(MgR₂) · M(diene) · m(polymer)⁻¹)⁻¹ ^(b))determined by ¹H NMR ^(b))determined by GPC in THF vs. PS standards. ^(d))determined by ¹³C NMR ^(e)) Nd:MgR = 1:1.5 ^(f))not determined because signals of functional groups are (partially) overlapped by backbone signals ^(g))not determined because the low amount of functional groups does not allow for a reliable integration.

¹³C-NMR shows all obtained polymers to be stereoregular with a high 1,4-trans-content (91-95 mol % trans-units), comparable to the model polymers obtained by activation of Nd(BH₄)₃.(THF)₃ with MgBu₂. NMR experiments verify the ability of this approach to generate polar functionalized chain-ends. All obtained polymers exhibit in both, ¹H and ¹³C NMR, characteristic signals for the respective functional group, including pyrrolidine rings for Mg-2, Mg-3, and Mg-4, resonating between δ=2.94 ppm (¹³C: 47.5 ppm, Mg-2) and 2.38 ppm (¹³C: 54.1 ppm, Mg-3). In addition, signals for the benzylic protons of Mg-3 (¹H: 3.53 ppm, ¹³C: 61.1 ppm) and (C₄H₈)N—CH₂ group of Mg-4 are found in the respective spectra. In the case of the PhS—CH₂— group, introduced by activation with Mg-5, a proton signal at δ=2.67 ppm (¹³C: 33.3 ppm) suggests functionalization and 1D-TOCSY reveals the connectivity along the residual pentyl-chain to the olefinic signal of the first unit in the PBD backbone. To further prove the chain-end functionalization, i.e. the attachment to the polymer chain, DOSY NMR experiments were performed for all different functional groups (FIG. 4). This verified a chain-end functionalization by showing that the functional groups have the same diffusion coefficients as the polymer backbone.

Chain-end functionalization proceeds efficiently for the obtained polymers. It is known that each activator MgR₂ transfers one moiety to the Nd center in the activation step. Moreover, MALDI-TOF analyses of the obtained polymers have proved that all polymer chains bear a chain-end with R-groups derived from the MgR₂ used. Under the assumption of quantitative chain-end functionalization, it is possible to determine the activation efficiency of the different Mg-x (Table 2). The activation efficiency is the ratio of the amount of functional groups found in the functionalized polymers to the theoretically expected amount of functionalization expected for quantitative activation of Nd(BH₄)₃.(THF)₃, i.e.

${{activation}\mspace{14mu} {efficiency}} = \frac{{mol}\mspace{14mu} \% \mspace{14mu} \left( {{{funct}.\mspace{14mu} {groups}}\mspace{14mu} {in}\mspace{14mu} {polymer}} \right)}{{mol}\mspace{14mu} \% \mspace{14mu} \left( {{\max.\mspace{14mu} {theoret}.\mspace{14mu} {amount}}\mspace{14mu} {of}\mspace{14mu} {{funct}.\mspace{14mu} {groups}}\mspace{14mu} {in}\mspace{14mu} {polymer}} \right)}$ ${{with}\mspace{14mu} {mol}\mspace{14mu} \% \mspace{14mu} \left( {{\max.\mspace{14mu} {theoret}.\mspace{14mu} {amount}}\mspace{14mu} {of}\mspace{14mu} {{funct}.\mspace{14mu} {groups}}\mspace{14mu} {in}\mspace{14mu} {polymer}} \right)} = \frac{{mmol}\mspace{14mu} \left( {{Mg}\text{-}x} \right)}{{mg}\mspace{14mu} \left( {{polymer}\mspace{14mu} {yield}} \right)\text{/}{mg}\mspace{14mu} {mmol}^{- 1}\mspace{14mu} \left( {{diene}\mspace{14mu} {monomer}} \right)}$

Activation occurs moderately for Mg-3 and Mg-4 with efficiencies between 42 and 58% (Mg-3) and 32 and 42% (Mg-4), respectively. In contrast, excellent activation efficiencies are observed for polymerizations activated with Mg-1 or Mg-5 (92-94%).

The molecular weight distributions are broader in these examples than observed for polymerizations activated with MgBu₂, this arises most likely from a slower activation compared to activation by MgBu₂ caused by the addition of Mg-x as a solid (the Mg-x used are typically poorly soluble in toluene). Nevertheless, molecular weights comparable to polymerizations activated with MgBu₂ can be obtained by adjusting the diene:Nd ratio. Polymerizations with a diene:Nd ratio of 920:1 gave polymers with molecular weights (48 and 57×103 g mol⁻¹) close to the theoretical value (50×103 g mol⁻¹, Table 2, entries 9 and 10).

Example 7

We have established separately that all three methods to functionalize the synthesized stereoregular poly(dienes) work. Further, it would be highly desirable to combine all three functionalization methods in one polymerization. This could give access to stereoregular, hetero-telechelic poly(dienes) bearing three different functional groups (Scheme 3).

Scheme 3: Combination of three different methods for the introduction of functional groups, thus enabling the synthesis of triple functionalized, hetero-telechelic poly(dienes).

Trifunctional Polymers.

Having established the functionalization of both end-groups and of the polymer backbone separately, we studied the combination of all three methods simultaneously to obtain hetero-telechelic, mid-chain functionalized poly(dienes).

As an example of a stereoregular poly(isoprene), the copolymerization of IP and 3 was investigated. The polymerization was activated with Mg-1 (IP:Nd:Mg=100:1:1) and quenched with Si(OEt)₄. The obtained polymer is stereoregular with 94% 1,4-trans-units. ¹H-NMR shows the presence of TMS-groups (0.19 ppm) and TMS₂NCH₂-groups (2.84 ppm) indicating a comonomer incorporation of 2.3 mol %. CarbNCH₂-groups resonate at 3.83 ppm and the aromatic protons of the carbazyl group are clearly observed (FIG. 5). The presence of 1 mol % of CarbN-groups derived from Mg-1 agrees excellently for the expected theoretical degree of functionalization (1 mol %) when quantitative chain-end functionalization is considered for the targeted degree of polymerization DP=100. 2D NMR-spectroscopy also reveals the presence of (EtO)₃Si-groups. While the proton resonance of the SiOCH₂CH₃ group is overlapped by the resonance of CarbNCH₂-groups (3.83 ppm), the presence of a signal at 59.0 ppm in the ¹³C dimension of the HSQC spectrum proves the functionalization of the other chain-end. However, as already observed in the quenching experiments above, the degree of functionalization is moderate (ca. 15-20% of the polymer chains). The connection of all three different functional groups to the polymer backbones was additionally verified by DOSY NMR.

Example 8

As an example of a stereoregular poly(butadiene), a copolymerization of BD and 6 (2 mol %) was studied. The polymerization was activated by Mg-5 (BD:Nd:Mg=100:1:1) and quenched with Si(OEt)₄ at the end of the reaction. ¹H, ¹³C, and 2D NMR spectroscopy shows the polymer obtained to be stereoregular (94% 1,4-trans-units) and reveals the presence of all three different functional groups (FIG. 6): PhS— groups originate from the activation of Nd(BH₄)₃.(THF)₃ with Mg-5 (¹H: 2.66 ppm, ¹³C: 33.2 ppm for PhS—CH₂-groups). Carbazol moieties (CarbN) introduced by direct copolymerization with 6 show characteristic shifts in the aromatic region (e.g. ¹H: 8.04 ppm, ¹³C: 120.5 ppm) and at 3.84 ppm (¹³C: 42.5 ppm) for CarbN-CH₂-groups. As already observed in the example above, the most characteristic proton resonance of the SiOCH₂CH₃ group (3.90 ppm) is (partially) overlapped by the resonance of CarbNCH₂-groups, but the presence of SiOCH₂CH₃-groups is proven by 2D NMR spectroscopy (¹³C: 59.0 ppm for SiOCH₂CH₃). A connectivity between all three different functional groups and the polymer backbone was unambiguously established by DOSY NMR FIG. 6).

Example 9

We have shown in previous work, that the direct copolymerization of functionalized dienes with butadiene or isoprene is feasible with cis-selective Nd-based catalyst systems. It would also be highly desirable for these systems to introduce the possibility of functionalizing chain-ends by activation with functionalized activators. Prior examples of the initiation of cis-selective butadiene polymerizations with magnesium alkyls are scarce. We tested the reported catalyst system (Nd(versatate)₃ activated with MgR₂ in the presence of ethylaluminium sesquichloride) in polymerizations of butadiene after activation with MgBu₂ or Mg-5. Polymerizations activated with MgBu₂ showed that the used catalyst system can produce stereoregular poly(butadiene) with a high content of 1,4-cis-units (e.g. 92 mol %). Similarly, a BD polymerization activated with Mg-5 resulted in the formation of stereoregular PBD (86 mol % 1,4-cis-units). Additionally, NMR spectroscopy reveals the presence of functional groups introduced by the activation with Mg-5 as already described above for trans-selective catalyst systems. These results evidence that the introduction of functionalized chain-ends by usage of functionalized activators is also feasible in cis-selective diene polymerization catalyzed by Nd-based catalyst systems. 

1. A stereoregular functionalized elastomer represented by poly(M1 co M2), wherein the functionalized elastomer comprises a microstructure selected from the group consisting of microstructures having at least 90 percent by weight of monomer residues in trans 1,4-configuration, and microstructures having at least 80 percent by weight of monomer residues in cis 1,4-configuration; wherein M1 is selected from the group consisting of isoprene and 1,3-butadiene; and M2 is of formula 4

wherein R⁶ is a covalent bond, phenylene, a linear or branched alkane diyl group containing 1 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; R⁷ is hydrogen or a linear or branched alkyl group containing 1 to 10 carbon atoms; X¹ is selected from formulas 5 and 6

wherein R⁸ and R⁹ are independently phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or one of R⁸ and R⁹ is hydrogen and the other is phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R⁸ and R⁹ taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; and X² is a sulfur atom or a structure of formula 7 or 8

wherein when X² is of formula 8, the S atom of formula 8 is adjacent to the phenyl ring of formula 6 and the N atom of formula 8 is adjacent to R⁶.
 2. The stereoregular functionalized elastomer of claim 1, wherein the functionalized elastomer comprises a microstructure selected from the group consisting of microstructures having at least 95 percent by weight of monomer residues in trans 1,4-configuration, and microstructures having at least 85 percent by weight of monomer residues in cis 1,4-configuration.
 3. The stereoregular functionalized elastomer of claim 1, wherein the elastomer comprises a one terminal end group of formula —R¹-Q, where R¹ is phenylene, or a linear or branched alkane diyl group containing 2 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; Q is of formula 2 or 3 —S—R²  2 where R² is phenyl, or a linear or branched alkyl group containing 2 to 10 carbon atoms; and

where R³ and R⁴ are independently phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R³ and R⁴ taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms.
 4. The stereoregular functionalized elastomer of claim 1, wherein the elastomer comprises a terminal end comprising a functional group selected from phosphane, phosphonic acid, phosphate, phosphodiester, phosphotriester, silyl, alklysilyl, alkoxysilyl, and siloxy.
 5. A rubber composition comprising the stereoregular functionalized elastomer of claim
 1. 6. A pneumatic tire comprising the rubber composition of claim
 5. 